Photosensitive medium comprising an aromatic protected aldehyde, a primary aromatic amine and a lower haloalkane



United States Patent 3,410,687 PHOTOSENSITIVE MEDIUM COMPRISING AN AROMATIC PROTECTED ALDEHYDE, A PRI- MARY. AROMATIC AMINE AND A LOWER HALOALKANE John Alan Mattor, Hollis, and Lawrence Price, Old Orchard Beach, Maine, assignors to Scott Paper Company, Delaware County, Pa., a corporation of Pennsylvania No Drawing. Continuation-impart of application Ser. No. 626,881, Mar. 29, 1967, which is a continuation-in-part of application Ser. No. 351,316, Mar. 12, 1964. This application Oct. 19, 1967, Ser. No. 676,637

6 Claims. (Cl. 9690) ABSTRACT OF THE DISCLOSURE A photographic medium or film comprises a lightpassing resinous binder containing as active ingredients (1) an aromatic protected aldehyde such as an aromatic cyclic acetal substituted on the benzene ring with at least one chromophoric group, (2) a primary aromatic amine and (3) a photosensitive lower haloa'lkane such as iodoform.

The medium, after being exposed to light, is developed or fixed simply by heating it which heating drives off enough of the chemicals in the background areas so that the background areas :are no longer light sensitive.

Related applications This application is a continuation-in-part of Ser. No. 626,881, Heat Development of Photographic Plate Containing Volatile Photosensitizer, filed Mar. 29', 1967, by the present inventors, which in turn was a continuation-inpart of Ser. No. 351,316, now abandoned, Photosensitive Medium Comprising a Furfurylidene, a Primary Aromatic Amine and a Lower Haloalkane, filed Mar. 12, 1964.

Background of the invention Application Ser. No. 351,316 discloses a photographic medium in which, under the influence of light and then heat, affurfural derivative, having a protected aldehyde structure is caused to react with a primary aromatic amine undenthe influence of a photosensitive haloalkane in such a manner that there is cleavage of the furan ring, and also of the protected aldehyde group to yield a complex Stenhouse dye structure that gives good dark or black images.

This invention It has now been found that the aromatic protected aldehyde type of structures, absent a furan ring, will react with primary aromatic amines when activated by photosensitive lower haloalkanes in a suitable plastic binder to produce dye structures of a wide variety of brilliant hues and colors, e.g., yellows, reds, greens and violets. These dye structures are Schiif bases, or their acid salts, and are therefore fundamentally different from the Stenhouse dye structures of the previous application, Ser. No. 351,316.

In brief compass, this invention is a photographic medium, especially in the form of a film applied from solvent solution, comprising a light-passing binder containing dispersed'therein in photographic amounts and proportions:

(a) Aphotosensitive lower ha-loalkane, e.g., ioidoform,

(b) A primary aromatic amine, e.g., 3,3-dimethoxy benzidene,

(c) An aromatic dye precursor having the structure:

ZRr wherein as indicated at X, the benzene ring contains at least one chromophoric group, which group is preferably in other than the ortho position. Y and Z can be oxygen, sulfur or nitrogen radicals, provided only one of them be a nitrogen. R and R are organic radicals such as aryl or alkyl radicals of preferably from 1 to 20 carbon atoms. R and R preferably jointly form acyclic acetal structure:

0 CH2 B A and B are any suitable radicals such as alkyl radicals having from 1 to 20 carbon atoms.

Generally, those primary aromatic amines that perform well in the photographic medium of the previous application, Ser. No. 351,316, work well in the present invention. While the benzene ring thereof can have additional substituents, it is preferred that a hydrogen occupy at least one position on the ring and in the case of the meta phenylene diamines that this position be para to a nitrogen group. The diamines are preferred, with the benzene ring preferably having at least one additional substituent.

The Schiff type dyes are produced in the photographic medium apparently by the action of an acid or acid moiety, produced from the haloalkane when it is exposed to light followed by heating, on the acid-sensitive aldehyde derivative to form an azo-methine (Schifi base) linkage. The haloalkane is believed to exist as a complex with the primary aromatic amine prior to exposure to light.

Other than the difference in the dye precursor that is used, the present photographic medium is similar to that of the previous application, Ser. No. 351,316, and is used in the same manner, i.e., the two photographic mediums can be applied to or impregnated within the same type of substrates, clear or opaque, from solvent solutions containing suitable binders. The exposure and heat development conditions are the same.

The images produced are brilliantly colored and have good density. The resolution of the medium is high. Image stability is good and the backgrounds are clear, which gives good contrast.

Preferred embodiments The table illustrates the chemical structures of Suitable protected aldehydes. Of these, the cyclic acetals might be said to be preferred both from the standpoints of their case of preparation and their performance. It will be noted that all compounds have a auxochromic grou such as -NO Cl, OH or dialkyl amino radicals attached to the benzene nucleus in either the meta or para position. In some cases the benzene ring is substituted more than once, in which case the other positions can he occupied.

Preferably the dye precursor is a crystalline solid at room temperature and has a melting point in the range of 40 to 225 C. It must of course be soluble in a suitable solvent system to permit it to be applied to a support with the other chemicals and the binder.

Examples (1) Compound 1, 0.1 g.; 4-aminodiphenylamine, 0.1 g.; and iodoforrn, 0.2 g. were dissolved in 6 ml. of 10% polystyrene in chloroform. This was coated on both subbed Mylar 1 film and subbed paper. After drying, the plates yielded red images on exposure to a carbon are through a negative in contact therewith followed by heating to 150 C. for 1.5 minutes.

(2) A coating formulation was prepared as in Example 1 using m-phenylenediamine in place of the 4-aminodiphenylamine. A green image resulted.

(3) Compound 2 was formulated in amounts ranging from 0.04 g. to 0.1 g., with iodoform ranging from 0.1 to 0.2 g., in 4.0 ml. of to percent polystyrene, with the following amines:

Amine Amount, g. Color of Image 2,4-diarninoethoxybenzene 0. 06 Rich brown. 3,3-dimethoxybenzidine 0. 08 Br lliant orange. 2,4-diaminoehlorobenze 0. 1 Br ght yellow. 4-aminodiphenylamine. 0. 1 Bright red.

Iodoforrn g 0.15 4-aminodiphenylamine g 0.10 Compound 13 g 0.10 Polystyrene (10%) in CHCl ml 10 It was coated on subbed paper with a Mayer bar, dried and exposed 15 seconds to a 7.7 k.v.a. carbon are at 18 inches. The exposed sheet was developed and fixed by heating. It gave a 10 step exposure on a conventional Stauffer step wedge.

(6) A plate was prepared from the following:

Compound 6 g 0.16 4-aminodiphenylamine g 0.2 Iodoform g 0.4 Polystyrene (10%) in CHCl ml 16 It was coated with a #20 Mayer bar on 21 subbed paper base, exposed for 15 seconds to a 7.7 k.v.a. carbon are at 18 inches through a negative in contact therewith, then heated to 270 F. in a circulating air oven for 1.5 minutes. The image was red-black.

(7) A transparency was prepared by coating a Mylar sheet, subbed with isotactic polystyrene, with Compound 4 g 0.10 3,3'dimethoxybenzidine g 0.20 Iodoform g 0.4 Polystyrene (10%) in CHCI ml 16 It was exposed for 35 seconds on the same are as above and heated in the same way.

Satisfactory images have been obtained from a variety of resinous binders, using various formulations of active 1 E. I. du Pont de Nemours Companys polyethylene terephthalate resin.

4 ingredients of the type above. Butvar (Monsanto), Vitel PE200 (Goodyear), VYHN (a vinyl chloride acetate copolymer by Union Carbide), Lucite 2009 (duPont), PPO (General Electric) all give useful results.

(8) Lacquer type coating mixtures were prepared with the following composition:

Polystyrene (Dow S-666 U) 0.6 Iodoform 0.1 Compound 1 0.1 Chloroform m 6 Amine:

(1) When one used g 0.1 (2) When two used (each) g 0.07

Amine Results (1) Blank (none) Faint pinkish image. (2) p-Bromo aniline Bright yellow. (3) 4,4'-thiodianiline Bright orange.

(4) 4,4-dithiodianiline (5) 4,4-sulionyldianiline (6) 5-rnethyl-2,4-t01uenediamine (7) m-Toluidine -Mustard (weak) Yellowish gray. Mustard.

(8) o-Anlsidme Yellowish gray.

(10) 3,5-diamino-4-chlorotoluene Bright orange.

(11) 2-fluoro-p-phenylenediamine Do.

(12) 1-ethoxy-2,4-diaminobenzene Brown.

(13) p-Ohlorophenoxy-2,4-diaminobenzene.. Orange-brown.

(14) Dodeeylmereapto-2,4-diaminobenzene- D0.

(15) 1-styryl-2,4-diaminobenzene Orange.

(16) 2,2"dichl0ro 5,5 dunathoxybenzidine. Do.

(17) O-tolidine 1. Orange-brown.

(18) l-chlor0-2,4diaminobenzene Orange-green.

(19) 4,4 oxydianiline Bright yellow.

(20) 2,6-dich1oro-p-phenylenedia Bright orange.

(21) 4,4 methylenedianiline. Mustard-yellow.

(22) 1-isopropy1-2,4-diaminob live.

(23) 3,3 dimethoxybenzidine. Intense carmine.

(24) 1chloro2,4-diaminobenzen Orange-brown.

(25) N-phenyl-p-phenylenediamine Intense Carmine.

(26) 4,4 diaminodiphenylarnine Deep purple-brown.

(27) 2,6dibromo-p-phenylenediamine. Good sepia.

(28) 2-bromo-p-phenylenediamine Do.

(29) m-Phenylenediamine Olive green.

(30) 2,4-toluenediamine Do.

(31) 2,6-dichlor0-p-phenylenediamine; 2,4,6 Grayish-orange.

tribromo 1,3-phenylene-diamine.

(32) 2,6-dichloro-p-phenylenediamine; 3,5 Orange.

dibromo-2,4-toluenediamine.

(33) 2,6 dichloro-p-phenylenediamlne; 3,3 Intense carmine.

dimethoxybenzidine.

(34) 3,5 dibromo 2,4-toluenediamine; 4,4 Olive green.

oxydianiline.

(35) 3,5 dibromo 2,4t0luenedian1ine; N-phenyl Deep earmine.

p-phenylenediamine.

(36) 3,5 dibromo 2,4-toluenediamine 3,3 Carmine.

dimethoxy benzidine.

(37) N -phenyl-p-phenylenediamine 2,6- Do.

dibrom0-p-pheuylenediamine.

(38) N-phenyl-p-phenylenediamine 2,4,6- Do.

tribromo-1-3,-phenylene-diamine. (39) N-phenyl-p-phenylenediamine 4,4-

REPRESENTATIVE AROMATIC DYE PRECURSORS OF THE PROTECTED ALDEHYDE TYPE Structure Melting point,

R 1 7647.5. (Guam-@011 o OC CHa 2(4-dimethy1aminophenyl)4,5,5-trimethy1-1,1,3-dioxane O-OH; CH; 2 (CHa)2-N-Cfi C 162-164.

O---CH2 N09 Bright yelloworange.

5 6 REPRESENTATIVE AROMATIC DYE PRECURSORS OF THE PROTECTED ALDEHYDE TYPEContinued Structure Melting Point O-CH2 H CH; 3 (cHer-N--0fi H3c c-N=c-@N 200402.

\O--C2 CH, @0112 -0112 on 4 NO 0 185.5-187.

@cfil o-wl NOa H 1130 Iii- 1H 5 NCfi cH,

HsC \O-{H/IIQ H502 Cl O-GHz CH3 6 \N CH 0 83-87.

HsC2 l OCz CHa O-CH2 CH5 7 C1 Cfi \C/ 55-56.

\OC: OHa

o-cm 0H, s @ofi o 48-50.

N62 o-cI in om o-cH, CH3 9 BIO-@Cfi \O/ White needles,

\ \CHl 134-136.

10 0-CH9 GHQ-O 0 @c C 13 O-GHz /CHa 11 N 0% /C\ 168-172.

O-GH: N 02 N O: 12 432K 170/30mm E O-GzH H;C\ /S' l2 2i 1a /N-CE 4445.5.

H3O SCi2 2| H3O 0- 12 2s White leaflets; 14 N O CH melt near room O temperature. H3O O-GnHzs We claim: Z are selected from the group consisting of oxygen, 1. A photographic medium comprising a light-passing sulfur and nitrogen radicals, provided only one of binder containing dispersed therein in photographic them be a nitrogen, and R and R are selected from amounts and proportions: the group consisting of aryl and alkyl radicals hav- (a) a photosensitive lower haloalkane, ing in the range of l to 20 carbon atoms each, said (b) a primary aromatic amine, dye precursor having a melting point in the range of (c) an aromatic dye precursor having the structure: 40 to 225 C.

X 2. The photographic medium of claim 1 wherein X is YR NO in the meta position. 3. The photographic medium of claim 1' wherein Y R and Z are oxygen radicals and R and R jointly form:

2 CH2 A wherein as indicated at X, the benzene ring contains at least one auxochromic group in other than the ortho position selected from the group consisting of B --NO Cl, -OH, and dialkyl amino radicals, Y and such that said dye precursor is a cyclic acetal, and where- 7 in A and B are individually selected from the group consisting of NO alkyl radicals having in the range of 1 to 20 carbon atoms and 4. The photographic medium of claim 1 wherein Y and Z are oxygen radicals and R and R jointly form:

-CH: A

-CH2/ \B such that said dye precursor is a cyclic acetal, and wherein A and B are OHr-O 8 5. The photographic medium of claim 1 wherein said lower haloalkane is iodoformv 6. The photographic medium of claim 3 wherein said primary aromatic amine is a anetaphenylene diamine which if substituted contains at least one hydrogen on the ring in the para position, and wherein said lower haloalkane is iodoform.

References Cited UNITED STATES PATENTS 6/1954 Martin u- 96100 6/1954 Martin 9610O UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,410,687 November 12, 1968 John Alan Mattor et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1 line 68 "benzidene" should read benzidine lines 2 to S, the formula should appear as shown below:

ZR Columns 3 and 4, structure No. l, the formula should appear as shc below: CH

OC-H CH 3 (CH N c\ C o----cH CH- 2(4'-dimethylaminophenyl)4,S,5trimethyl-l,S-dioxane Columns 5 and 6, formula No. 10, should appear as shown below:

NO o-cH CH o \OCH2 \CHZ o/ Column 5, lines 66 to 70, the formula should appear as shown bel same column 5, line 75, "C1," should read C1-,

Signed and sealed this 16th day of February 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR Attesting Officer Commissioner of Patents 

